Api publ 4704 2001 (american petroleum institute)

20005-4070 Institute 202-682-8000 Characterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion Sources Regulatory and

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American 1220 L Street, Northwest

PetrOkUm Washington, D.C 20005-4070

Institute 202-682-8000

Characterization of Fine Particulate

Emission Factors and Speciation

Profiles from Stationary Petroleum

Industry Combustion Sources

Regulatory and Scientific Affairs

PUBLICATION NUMBER 4704

AUGUST 2001

Copyright American Petroleum Institute

Reproduced by IHS under license with API

Not for Resale

No reproduction or networking permitted without license from IHS

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`,,,,`,-`-`,,`,,`,`,,` -Copyright American Petroleum Institute

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Gas Fired Heater-Test Report

Characterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion Sources

Regulatory and Scientific Affairs

API PUBLICATION NUMBER 4704 AUGUST 2001

PREPARED UNDER CONTRACT BY:

GE ENERGY AND ENVIRONMENTAL RESEARCH CORPORATION

18 MASON IRVINE, CA 9261 8

American Petroleum Institute

Not for Resale

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`,,,,`,-`-`,,`,,`,`,,` -FOREWORD

API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED

API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANUFAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS

NOTHING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PATENT NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LETTERS PATENT

THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL-

means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the

publisher Contact the publisher; APIPublishing Services, I220 L Street, N K, Washington, D.C 20005

Copyright O 2001 American Petroleum Institute

II

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GE ENERGY AND ENVIRONMENTAL RESEARCH CORPORATION

PROJECT TEAM MEMBERS Glenn England, Project Manager Stephanie Wien, Project Engineer Bob Zimperman, Field Team Leader Barbara Zielinska, Desert Research Institute Jake McDonald, Desert Research Institute

111

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02, COZ, CO, NOx AND SO2 3 1

IN-STACK METHOD TESTS 3-5

In-Stack Total Filterable PM, PM10 and PM2.5 3-6

Condensible Particulate Matter Mass and Chemical Analysis 3 1 1

DILUTION TUNNEL TESTS 3-14

PM2.5 Mass 3-16

Elements 3 16

Sulfate, Nitrate, Chloride and Ammonium 3 17

Organic and Elemental Carbon 3-18

Volatile Organic Compounds 3 19

Semivolatile Organic Compounds 3-19

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`,,,,`,-`-`,,`,,`,`,,` -TABLE OF CONTENTS (CONTINUED)

4.0 TEST RESULTS 4-1

PROCESS OPERATING CONDITIONS 4 1

PRELIMINARY TEST RESULTS 4-4

STACK GAS CONDITIONS AND FLOW RATE 4-4

CO, NO, AND SO2 EMISSIONS 4-4

IN-STACK AND IMPINGER METHOD RESULTS 4.6

Particulate Mass 4.6

OC EC and SVOCs 4-9

DILUTION TUNNEL RESULTS 4 1 1

Particulate Mass 4 1 1

Sulfate, Chloride Nitrate and Ammonium 4 12

OC EC and Organic Species 4 13

Elements 4 17 5.0 EMISSIONS FACTORS AND SPECIFICATION PROFILES 5 1

SAMPLE STORAGE AND SHIPPING 6 1

DILUTION TUNNEL FLOWS 6 1

GRAVIMETRIC ANALYSIS 6 1

Dilution Tunnel Filters 6 1

In-Stack Filters 6-3

ELEMENTAL (XRF) ANALYSIS 6.4

ORGANIC AND ELEMENTAL CARBON ANALYSIS 6-5

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`,,,,`,-`-`,,`,,`,`,,` -TABLE OF CONTENTS (CONTINUED)

SVOC ANALYSIS 6-7 VOC ANALYSIS 6-9 CEMS ANALYSIS 6 12 DISCUSSION AND FINDINGS 7-1

PM2.5 MASS MEASUREMENTS 7 1 CHEMICAL SPECIATION OF PRIMARY PM2.5 EMISSIONS 7.5 SECONDARY PM2.5 PRECURSOR EMISSIONS 7.9 7.0

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PM2.5/PM 1 O Train Configuration for Method 20 1 A/202 3-7 Method 201A (Modified) Sample Recovery Procedure 3-8 Method 201A (Modified) Sample Analysis Procedure 3-9 Sampling Train configuration for EPA Method 17 3-10 Method 202 Sample Recovery Procedure 3-12 Method 202 Sample Analysis Procedure (Modified) 3 13 Dilution Tunnel Sampling System 3-15 PM2.5 Speciation Profile for Gas-Fired Process Heater - Dilution Tunnel

Results (Refinery Site B) 5-9 PM2.5 Speciation Profile for Gas-Fired Process Heater - Method 201/202

Results (Refinery Site B) 5-11 SVOC Speciation Profile for Gas-Fired Process Heater - Dilution Tunnel

Results (Refinery Site B) 5-14 Method 202 Inorganic Fraction Residue Analysis

for Gas-Fired Process Heater Tests (Refinery Site B) 7-2 Results of Laboratory Tests Showing Effect of SO2 and Purge on Method 202

Sulfate Bias 7-4 In-Stack and Ambient Species Concentrations For Gas-Fired Process Heater -

Dilution Tunnel Results (Refinery Site B) 7-6 Comparison of Species Concentrations to Detection Limits for Gas-Fired

Process Heater - Dilution Tunnel Results (Refinery Site B) 7-7 Mean Species Concentrations and Standard Deviation for Gas-Fired Process

Heater Tests - Dilution Tunnel Results (Refinery Site B) 7-8

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Process Heater e5-5 Summary of Secondary Particulate Precursor Emission Factors for Gas-Fired

Process Heater e5-7 Substances of Interest not Detected in Stack Emissions from Gas-Fired

Process Heater e5-8 Overview of Sampling Scope 1-3 Summary of Analytical Targets l -4

Overview of Sampling Scope 2-2 Summary of Analytical Targets 2.3 Summary of Test Procedures 3-2 CEMS Instrumentation Used for Gas-Fired Process Heater Test (Refinery

Site B) 3-5 Approximate In-Stack Detection Limits Achieved for Gas-Fired Process

Heater Tests (Refinery Site B) 4-2 Process Operating Conditions for Gas-Fired Process Heater (Refinery Site B) 4.3 Fuel Gas Analysis for Gas-Fired Process Heater Tests (Refinery Site B) 4-3 Average Stack Gas Parameters for Gas-Fired Process Heater Tests

Not for Resale

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`,,,,`,-`-`,,`,,`,`,,` -LIST OF TABLES (CONTINUED)

Gas-Fired Process Heater (Refinery Site B) 4- 13 Dilution Tunnel Organic and Elemental Carbon Results for Gas-Fired

Process Heater (Refinery Site B) 4- 14 Dilution Tunnel SVOC Results for Gas-Fired Process Heater (Refinery

Site B, mg/dscm) 4- 15 Dilution Tunnel VOC Results for Gas-Fired Process Heater (Refinery Site B) .4- 1 8

Dilution Tunnel Elemental Results for Gas-Fired Process Heater (Refinery Site B) 4- 19 Particulate Mass, Element, and Ion Emission Factors for Gas-Fired Process

Heater (Refinery Site B) 5-2 Carbon and Semivolatile Organic Compound Emission Factors for Gas-

Fired Process Heater (Refinery Site B) 5-3 Volatile Organic Compound Emission Factors for Gas-Fired Process

Heater (Refinery Site B) 5-6

NO, and SO2 Emission Factors for Gas-Fired Process Heater (Refinery

Site B) 5-8 PM2.5 Speciation Profile for Gas-Fired Process Heater - Dilution Tunnel

Results (Refinery Site B) 5-8 PM2.5 Speciation Profile for Gas-Fired Process Heater - Method 201N202

Results (Refinery Site B) .5- 1 O

SVOC Speciation Profile for Gas-Fired Process Heater - Dilution Tunnel Results (Refinery Site B) .5- 12

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`,,,,`,-`-`,,`,,`,`,,` -LIST OF TABLES (CONTINUED)

Table

6- 1

6-2 6-3 6-4 6-5

6-6 6-7 6-8

Pre- and Post-test Flow Checks for Dilution Tunnel for Gas-Fired Process Heater Tests (Refinery Site B) 6-2

Method 20 M 2 0 2 Blank Results .6-3

Acetone Blank Results for Gas-Fired Process Heater (Refinery Site B) .6-4

Blank Results for Elements .6-5

Organic and Elemental Carbon Blank Results for Gas-Fired Process Heater (Refinery Site B) 6-6

Ion Blank Results .6-7

SVOC Blank and Replicate Results .6- 1 O

VOC Blank Results .6- 1 1

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EXECUTIVE SUMMARY

In 1997, the United States Environmental Protection Agency (EPA) promulgated new ambient

air standards for particulate matter smaller than 2.5 micrometers in diameter (PM2.5) Source

emissions data are needed to assess the contribution of petroleum industry combustion sources to ambient PM2.5 concentrations for receptor modeling and PM2.5 standard attainment strategy

development There are few existing data on emissions and characteristics of fine aerosols from petroleum industry combustion sources, and the limited information that is available is

incomplete and outdated The American Petroleum Institute (API) developed a test protocol to

address this data gap, specifically to:

Develop emission factors and speciation profiles for emissions of primary fine particulate matter (i.e., particulate present in the stack flue gas including condensible aerosols), especially organic aerosols from gas-fired combustion devices; and

Identi@ and characterize secondary particulate (i.e., particulate formed via reaction of stack emissions in the atmosphere) precursor emissions

This report presents results of a pilot project to evaluate the test protocol on a 1 14 million British

thermal unit (MMBtu) per hour gas-fired refinery process heater The process heater has a

refractory-lined rectangular box furnace with a single row of burners on two opposing sides of

the furnace with a tubular process fluid heat exchanger located at the top of the furnace The unit has no controls for NO, emissions The flue gas temperatwe at the stack was approximately

680°F during the tests

The particulate measurements at the stack were made using both a dilution tunnel research test

method and traditional methods for regulatory enforcement of particulate regulations The

dilution tunnel method is attractive because the sample collection media and analysis methods

are identical to those used for ambient air sampling Thus, the results are directly comparable

with ambient air data Also, the dilution tunnel method is believed to provide representative

results for condensible aerosols Regulatory methods are attractive because they are readily

accepted by regulatory agencies and have been used extensively on a wide variety of source

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`,,,,`,-`-`,,`,,`,`,,` -types; existing regulatory methods for condensible aerosols may be subject to significant bias, however, and sampling/analytical options are limited

Emission factors for all species measured were extremely low, which is expected for gas-fired

sources Emission factors for primary particulate, including: total particulate, PM 1 O (particles

smaller than nominally 10 micrometers), and PM2.5; elements; ionic species; and organic and elemental carbon are presented in Table E- 1 Since the process heater was firing refinery process gas with a heating value different from natwal gas, emission factors are expressed in pounds of pollutant per million British thermal units of gas fired (lb/MMBtu) All tests were performed in triplicate As a measure of the bias, precision, and variability of the results, the uncertainty and 95% confidence upper bound also are presented

Emission factors for semi-volatile organic species are presented in Table E-2 The sum of semivolatile organic species is approximately 3% of the organic carbon Emission factors for

secondary particulate precursors (NO,, S02, and volatile organic species with carbon number of

7 or greater) are presented in Table E-3

The preceding tables include only those substances that were detected in at least one of the three test runs Substances of interest that were not present above the minimum detection limit for these tests are listed in Table E-4

A single ambient air sample was collected at the site In some cases, the emission factors

reported in Tables E-1 to E-3 resulted from in-stack concentrations that were near ambient air concentrations Those in-stack species concentrations that are within a factor of 10 of the

ambient air concentration are indicated on the table by an asterisk (*)

The primary particulate results presented in Table E-1 also may be expressed as a PM2.5

speciation profile, which is the mass fraction of each species contributing to the total PM2.5 mass The speciation profile is presented in Figure E-1

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`,,,,`,-`-`,,`,,`,`,,` -The main findings of these tests are:

Particulate mass emissions from the process heater were extremely low, consistent with levels expected for gaseous fuel combustion

Two methods for determining the average emission factor for primary PM2.5 mass

gave results which differed in magnitude by a factor of 89:0.000054 IbíMMBtu using the dilution tunnel; and 0.0048 IbíMMBtu using conventional in-stack methods for

filterable and condensible particulate

Sampling and analytical artifacts principally caused by gaseous SO2 in the stack gas

were shown to produce a relatively large positive bias in condensible particulate as measured by conventional in-stack methods Most of the difference between the dilution tunnel and conventional method results can be explained by these measurement artifacts The results using conventional EPA methods are nominally consistent with published EPA emission factors for external combustion of natwal gas (U S EPA, 1998) Therefore, the published EPA emission factors derived from tests using similar measurement methods also may be positively biased

Chemical species accounting for 100% of the measured PM2.5 mass were quantified

Organic and elemental carbon comprise 49% of the measured primary PM2.5 mass

Sulfate, ammonium, chloride and nitrate together account for approximately 32% of the measured PM2.5 mass; sulfate alone accounts for approximately 22%

Cobalt, calcium, silicon, copper, zinc, iron, aluminum and lanthanum account for

approximately 17% of the measured PM2.5 mass Smaller amounts of ten other

detected elements comprise the remaining 2%

Most elements are not present at levels significantly above the background levels in the ambient air or the minimum detection limits of the test methods

Most organic species are not detected at levels significantly above background levels

in the ambient air or field blanks All detected organics are present at extremely low levels consistent with gaseous fuel combustion

Emissions of secondary particle precursors are low and consistent with levels expected for gaseous fuel combustion

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`,,,,`,-`-`,,`,,`,`,,` -Table E- 1 Summary of Primary Particulate Emission E

Substance

'articulate Condensible Particulate (inorganic) víass I Condensible Particulate (organic)

Total condensible particulate '

Total Filterable PM (in-stack method)

PM2.5 (Dilution Tunnel) Aluminum

Barium Bromine Calcium Chlorine Chromium Cobalt Copper Iron Lanthanum Magnesium Manganese Nickel Phosphorous Potassium Silicon sodium Strontium Sulfur Zinc Chloride Nitrate Sulfate Ammonium Organic Carbon (dilution tunnel) Elemental Carbon (dilution tunnel) Total Carbon (dilution tunnel)

4.8E-3 2.4E-4 4.6E-3

1 OE-3 6.4E-4 2.2E-4 4.8E-3 5.4E-5 8.7E-7 5.6E-7 1.1E-8 1.9E-6 1.9E-6 2.6E-8 3.8E-6 1.3E-6 1.1E-6 7.1E-7 8.1E-8 5.9E-8 5.9E-8 9.8E-8 2.7E-7 1.4E-6

1 OE-7 2.8E-8 3.3E-6 1.1E-6 2.7E-6 1.1E-6 1.5E-5 3.3E-6 2.8E-5 1.9E-5 3.4E-5

Process He:

Uncertainty (%)

1 OE-3 3.1E-4

1 %-4 2.2E-6 1.1E-6

d a 5.6E-6 1.2E-5

d a 1.5E-5 2.3E-6 3.1E-6

d a

d a 2.2E-7 1.2E-7 1.8E-7 6.8E-7 4.1E-6

d a

d a 9.6E-6 2.6E-6 9.8E-6

d a 8.9E-5 1.5E-5 4.5E-5

d a 6.8E-5

* <lox ambient (1) <lox detection limit, ambient = ND

(2) Sum of total condensible PM and filterable PM2.5

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`,,,,`,-`-`,,`,,`,`,,` -Table E-2 Summary of Semi-volatile Organic Species Emission Factors for Gas-Fired Process Heater

Dilution Tunnel

(1’

Substance Coronene

2 -methylbiphenyl 3-methylbiphenyl Phenanthrene 9-fluorenone

2 -methylnaphthalene C-methylphenanthrene Acenaphthenequinone Fluoranthene

A-methylfluorene

1 -methylnaphthalene

1 -methylfluorene B-methylphenanthrene

1,3+1,6+1,7-dimethylnaphthalene

Benzo(b+j+l)fluoranthene

C-dimethylphenanthrene

2 -methylphenanthrene 4-methylbiphenyl B-dimethylphenanthrene Pyrene

2,6+2,7-dimethylnaphthalene

Benz(a)anthracene-7,12 9-methylanthracene Benzo(b)chrysene 2,3,5 +I-trimethylnaphthalene

1,2&trimethylnaphthalene

C-trimethylnaphthalene Benzanthrone

Anthrone A-dimethylp henanthrene A-trimethylnaphthalene Dibenz(ah+ac)anthracene B-trimethylnaphthalene Anthracene

F-trimethylnaphthalene Indeno[ 123-cdlpyrene Benzo(a)pyrene Benzo(ghi)perylene

7 -methylbenzo( a)pyrene E-trimethylnaphthalene

1 -methylphenanthrene Chrysene

4-methylp yrene

Bem( a)anthracene Anthraquinone

1 -ethyl-2-methylnaphthalene 1,7-dimethylphenanthrene

B-methylp yrenelme thyl fluorene E-methylp yrenelme thyl fluorene 9,l O-dihydrobenzo(a)pyrene 9-anthraldehvde

1,4-chrysenc&none

<lox detection limit ambient = ND

Emis sion Factor (lb/MMBtu) 1.6E-7 8.3E-8 5.7E-8 5.2E-8 4.9E-8 4.5E-8 4.3E-8 3.9E-8 3.8E-8 3.6E-8 2.6E-8 2.2E-8 2.1E-8 2.1E-8 1.5E-8 1.5E-8 1.4E-8 1.4E-8 1.4E-8 1.3E-8

l l E - 8

1 OE-8

1 OE-8 9.8E-9 8.2E-9 8.1E-9 7.6E-9 7.3E-9 6.9E-9 6.8E-9 6.8E-9 6.3E-9 5.9E-9 5.1E-9 5.OE-9 4.7E-9 4.6E-9 4.5E-9 4.4E-9 4.1E-9 4.OE-9 3.8E-9 3.8E-9 3.7E-9 3.1E-9 3.OE-9 2.9E-9 2.8E-9 2.8E-9 2.6E-9 2.5E-9

d a 6.1E-8 5.OE-8 2.3E-8 1.9E-8

d a .5E-8 6E-8 2E-8

d a .2E-8 4E-8 OE-8 1.3E-8

1 OE-8

l l E - 8 9.9E-9

l l E - 8 1.4E-8 8.2E-9 1.5E-8 8.OE-9 7.4E-9

1 OE-8

d a 7.2E-9 5.7E-9 1.2E-8 1.6E-8 6.7E-9

d a 5.3E-9 (2) <lox detection limit, blank = ND

Not for Resale

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`,,,,`,-`-`,,`,,`,`,,` -Table E-2 (continued) Summary of Semi-volatile Organic Species Emission Factors for Gas- Fired Process Heater

Dilution Tunnel

In-Stack Filter

(1:

Substance Benzonaphthothiophene

1 -methylfluorene+C-inethylp yrene/methylfluorene

1 -phenylnaphthalene Benzo( c)phenanthrene Perylene

4H-cyclopenta(def)phenanthrene

Benzo(e)pyrene

5 +6 -methylchry sene

1 -methylpyrene D-methylp yrene/methy lfluorene

2 -phenylnaphthalene

Sum of All SVOCs

1,2,8 -trimethylnaphthalene 1,4-~hrysenequinone 2,6+2,7 -dimethylnaphthalene

2 -methylphenanthrene 4-methylbiphenyl Benzo(a)pyrene Benzo(b) chry sene Biphenyl

Sum of All SVOCs

4 Ox detection limit, ambient=ND

Emission Factor JbíMMBtu) 2.4E-9 2.1E-9 2.1E-9 1.6E-9 1.5E-9 1.3E-9 1.2E-9 9.6E- 1 O

7.9E- 1 O

5.1 E-1 O

2.5E- 1 O

6.6E-7 7.2E-10 2.5E-9 6.8E-9 1.4E-9 1.9E-9 2.6E-9 2.6E-9 7.7E-9

d a

d a 5.7E-9 4.3E-9 3.5E-9 2.2E-9 2.7E-9

d a 9.9E- 1 O

d a

(2) 4 Ox detection limit, blank = ND

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`,,,,`,-`-`,,`,,`,`,,` -Table ES-3 Summary of Secondary Particulate Precursor Emission Factors for Gas-Fired

Refinery Process Heater

Gases Volatile Compounds organic

Substance so*

NO"

1+7 hexadecene

1,2,3,4-tetrarnethylbenzene (1) 1,2,4 trimethylbenzene * 1,3,5 trimethylbenzene * 1,3-dichiorobenzene * 1-methylnaphthalene * 2-methyl octane * 2-methylnaphthalene * 3-methyl octane * Acetophenone Benzaldehyde * Benzofuran Benzonitrile Biphenyl c12 hydrocarbon it (1) c12 hydrocarbon 2 t (1) c12 hydrocarbon 3 t (1) c12 hydrocarbon 4 t (1)

c 13 hydrocarbon 1 t

c14 hydrocarbon it

Ethyl benzene * m- & p-xylenes * m-ethyltoluene * n-decane * n-dodecane * n-eicosane n-heptadecene n-hexadecene n-nonadecane n-nonane * n-octadecane n-pentadecane * n-propylbenzene * n-tetradecane * n-tridecane n-undecane Naphthalene * Nonanol * o-ethyltoluene * o-xylene * p-ethyltoluene * Phenol

Styrene

'mission Factor (lb/MMBtu) l.lE-3 1.7E-1 1.9E-4 4.4E-7 1.3E-6 4.3E-7 1.2E-6 5.2E-7 1.2E-6 5.2E-7 4.1E-7 6.6E-5 4.2E-5 1.5E-6 1.6E-5 7.6E-7 4.3E-6 1.2E-6 3.5E-6 1.5E-6 3.6E-6 1.3E-6 9.8E-7 3.1E-6 7.4E-7 4.8E-7 8.5E-7 9.9E-7 9.6E-7 1.5E-6 2.OE-6 9.8E-7

1 OE-6 9.7E-7 3.1E-7 1.4E-6 2.5E-6 4.3E-6 9.3E-7 3.2E-7 3.4E-7 1.4E-6 3.4E-7 2.8E-5 3.8E-6

Uncertainty (%)

1 OE-4 4.OE-6 4.7E-5

d a 7.3E-6 3.9E-6 1.3E-5 5.OE-6 1.6E-5 3.1E-6 1.4E-6 5.OE-6

1 OE-6 1.3E-6 1.9E-6

2 SE-6 2.8E-6

d a 8.9E-6 2.OE-6 2.8E-6 2.2E-6 5.9E-7 2.9E-6 7.8E-6 1.5E-5 2.7E-6

d a 6.6E-7 2.OE-6 4.9E-7 8.4E-5 7.6E-6

* <lox ambient (1) <lox detection limit, ambient = ND

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`,,,,`,-`-`,,`,,`,`,,` -Table E-4 Substances of Interest Not Detected in Stack Emissions from Gas-Fired Process Heater

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Section 1

PROJECT DESCRIPTION

PROJECT OVERVIEW

In 1997, the United States Environmental Protection Agency (EPA) promulgated new ambient

air standards for particulate matter, including for the first time particles with aerodynamic

diameter smaller than 2.5 micrometers (PM2.5) There are few existing data regarding emissions and characteristics of fine aerosols from petroleum industry combustion sources, and such

information that is available is fairly old Traditional stationary source air emission sampling methods tend to underestimate or overestimate the contribution of the source to ambient aerosols because they do not properly account for primary aerosol formation, which occurs after the gases leave the stack This issue was extensively reviewed by API in a recent report (England et al.,

1997), which concluded that dilution sampling techniques are more appropriate for obtaining a

representative sample from combustion systems These techniques have been widely used in

research studies (Hildemann et al., 1994; McDonald et al., 1998), and use clean ambient air to dilute the stack gas sample and provide 80-90 seconds residence time for aerosol formation prior

to sample collection for determination of mass and chemical speciation

As a result of the API review, a test protocol was developed based on the dilution sampling system described in this report The dilution sampling protocol was used to collect particulate emissions data from petroleum industry combustion sources, along with emissions data obtained from conventional sampling methods This test program is designed to provide reliable source emissions data for use in assessing the contribution of petroleum industry combustion sources to ambient PM2.5 concentrations The goals of this test program were to:

Develop emission factors and speciation profiles for emissions of fine particulate matter, especially organic aerosols;

Identi@ and characterize PM2.5 precursor compound emissions

This test report describes the results of tests performed on a gas-fired process heater at Refinery Site B on October 13, 14 and 15, 1998

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Characterize key secondary particle precursors in stack gas samples: volatile organic compounds (VOC) with carbon number of 7 and above; sulfur dioxide (S02); and oxides of nitrogen (NOX);

Document the relevant process design characteristics and operating conditions during the test

in Table 1-2 Heater process data and fuel gas samples were collected during the tests to

document operating conditions

Source Level (In-stack) Samples

In-stack sampling and analysis for filterable (total, PM10 and PM2.5) and condensible

particulate matter (CPM), NO,, oxygen (Oz), carbon dioxide (COZ), carbon monoxide (CO) and SO2 was performed using traditional EPA methods In-stack cyclones and filters were used for filterable particulate matter Sample analysis was expanded to include OC, EC and organic species on the in-stack quartz filters

1-2

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`,,,,`,-`-`,,`,,`,`,,` -Sampling Test Methods Number of Samples at Each Sampling Location

Stack EPA Method 201N202 Train

EPA Method 17 Train

Dilution tunnel

Teflon@ filter TIGF/PUF/XAD-4 Quartz filter

Tenax

3

Fuel Gas Heater

XAD-4 = Amberlitem sorbent resin

Dilution Stack Gas Samples

Dilution sampling was used to characterize PM2.5 including aerosols formed in the near-field plume The dilution sampler extracted a sample stream from the stack into a mixing chamber, where it was diluted approximately 13: 1 with purified ambient air Because PM2.5 behaves aerodynamically like a gas at typical stack conditions, the samples were extracted

nonisokinetically A slipstream of the mixed and diluted sample was extracted into a residence

time chamber where it resided for approximately 80 seconds to allow time for low-concentration

aerosols, especially organics, to condense and grow The diluted and aged sample then passed through cyclone separators sized to remove particles larger than 2.5 microns, after which

samples were collected on various media: high-purity quartz, Teflon@ membrane filter (TMF), and Teflon@-impregnated glass fiber (TIGF) filters; a polyurethane foam (PUF)/Amberlite@ sorbent resin (XAD-4)PUF cartridge to collect gas phase semivolatile organic compounds; and a Tenax cartridge to capture VOCs Three samples were collected on three sequential test days

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`,,,,`,-`-`,,`,,`,`,,` -Table 1-2 Summary of Analytical Targets

TMF = Teflon@ membrane filter TIGF = Teflon@-impregnated glass fiber filter

*Carbon number of 7 or greater

An ambient air sample was collected to establish background concentrations of measured substances The same sampling and analysis procedures used for the dilution tunnel were applied for collecting ambient air samples

Process Samples

A sample of the fuel gas burned in the process heater was collected on each day of testing and analyzed for specific gravity, heating value, and hydrocarbon speciation Samples of liquid hydrocarbon from the fuel gas knockout drum were planned; however, there was no liquid accumulation during the tests

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`,,,,`,-`-`,,`,,`,`,,` -KEY PERSONNEL

GE Energy and Environmental Research Corporation (GE EER) had primary responsibility for

the test program Key personnel involved in the tests were:

Glenn England (GE EER) - Program Manager (949) 859-885 1

Stephanie Wien (GE EER) - Project Engineer (949) 552- 1803

Bob Zimperman (GE EER) - Field Team Leader (949) 552-1 803

Barbara Zielinska (Desert Research Institute) - Dilution Sampling and

Not for Resale

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Section 2

PROCESS DESCRIPTION

The tests were performed on a gas-fired process heater at Refinery Site B The heater has a

maximum firing rate of 114 MMBtu/hr with a typical rate of approximately 70 MMBtuh The

unit is made up of 4 box-type heaters, with 30 burners on each side in an opposed fired

configuration (60 per box), vented to a common stack Each furnace is radiant-wall fired, and all

four share one common convection coil The heater is fired on refinery fuel gas and is a low

temperature duty design with a typical furnace temperature of approximately 1500°F The unit is

not equipped with air pollution controls for NO,, SO, or particulate The heater appeared to be

in good working condition during the test Operating conditions during the test are given in

Section 4 Process parameters monitored during testing include: fuel gas flow rate, specific

gravity, heating value and H,S content; process fluid flow rate; process fluid outlet temperature;

excess oxygen; and burners in service (in or out)

SAMPLING LOCATIONS

Figure 2- 1 provides an overview of the boiler process and the sampling and monitoring

locations Flue gas samples were collected from the stack The single stack is equipped with a

360-degree sampling platform located 100 feet above the ground, which is accessible via a

ladder There are four threaded 4-inch diameter sampling ports with 4-inch pipe nipples welded

to the stack, located orthogonally around the circumference approximately 52 inches above the

platform The stack diameter at this elevation is 74.3 inches The sample ports are located 630

inches (8.5 diameters) downstream and 304 inches (4.1 diameters) upstream of the nearest flow

disturbances Following velocity and 0, traverses to check for stratification, all sampling was

performed at a single point in the center of the stack to facilitate Co-location of the dilution

tunnel and EPA Method 201N202 probes

Fuel gas samples were collected from the gas supply fuel-sampling manifold Ambient air

samples were collected at near ground level close to the process heater

2- 1

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`,,,,`,-`-`,,`,,`,`,,` -Refine Gas

Sampling location

s 1

s 2

s 3 M1 M2A, M2B M3

M4A, M4B M5

Stack Ground level Fuel gas feed Fuel gas header Fuel gas feed Heater flue gas outlet Process fluid feed Stack

Heater 2

T

Approximately

15 ft Furnace Cross Section

3umei

Parameters See Table 4-1

Specific gravity, H2S, Btu content Fuel gas flow rate

Excess oxygen Process fluid flow rate, process fluid Flue gas temperature

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`,,,,`,-`-`,,`,,`,`,,` -Section 3

TEST PROCEDURES

An overview of the sampling and analysis procedures is given in Table 3- 1 Figure 3- 1 shows

the testing chronology for the dilution tunnel and in-stack methods The time of day for the start and finish of each measurement run is shown on the figure For example, Method 201N202 Run

1 began at 1 3 5 1 hours and finished at 195 1 hours on Tuesday, October 13 Dilution tunnel

testing and in-stack testing were performed concurrently All samples were collected at

approximately the same point in the center of the stack; the dilution tunnel and in-stack test method probes were Co-located

STACK GAS FLOW RATE, MOISTURE CONTENT AND MOLECULAR WEIGHT

An S-type Pitot tube (EPA Method 2) was used to determine the average stack gas velocity and

volumetric flow rate Stack gas molecular weight was calculated in accordance with EPA

Method 3 Moisture content of the sample was determined based on weight gain of the

impingers used in the Method 201N202 train according to EPA Method 4 A full velocity traverse of the stack was performed before and after each test to determine total stack gas flow rate

02, COZ, CO, NO, AND SO2

Major gases and pollutant concentrations in the stack sample were measured using a continuous

emission monitoring system (CEMS), illustrated schematically in Figure 3-2 Table 3-2 lists the

CEMS specifications The sample was collected from a single traverse point in the stack after

verifying that the gas concentration profile deviated by less than 1 O percent of the mean

concentration Sample gas was passed through a primary in-stack sintered metal filter, a heated stainless steel probe, a heated Teflon@ transfer line, a primary moisture removal system (heat exchanger impingers in an ice bath), a heated secondary filter, a diaphragm pump, and a heated back-pressure regulator to a thermoelectric water condenser The condenser’s heat exchangers are specially designed impingers that separate the condensate from the gas sample with a

3-1

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`,,,,`,-`-`,,`,,`,`,,` -Table 3-1 Summary of Test Procedures

Sampling Location

j l (Stack)

Measurements Sampling

Approach In-stack series cyclones and Total PM, PM 1 O,

PM2.5 and filter composition

PM composition In-stack filter Condensible PM and Impingers composition

Gaseous PM2.5 Continuous Precursors

PM2.5 mass and chemical composition

Dilution tunnel and filters

Sample Analyses Mass; organic species

Organic carbon, elemental carbon

Mass (organic and inorganic), sulfate, chloride, nitrate,

aiockout drum)

Reference U.S EPA Method 201A (modified)

U S EPA Method 17

(modified) U.S EPA Method 202 (modified)

j2 (Ground Level -

h b i e n t Air)

ammonium, elements

SOz and NO, (Oz, COz, CO IU S EPA Methods

VOC Dilution tunnel and Tenax

svoc filter/PUFBiAD-4/PUF PM2.5 and chemical Filters

composition

Dilution tunnel and

sulfate, nitrate, chloride,

Zielinska et al., 1996;

Speciated SVOC Mass, organic carbon, elemental carbon, organic species, elements, chloride, sulfate, nitrate, ammonium Speciated VOC

Speciated SVOC Hydrocarbon speciation and

Speciated VOC IHildemann et al., 1989

1U.S EPA Method T013; Hildemann et al., 1989 U.S EPA, 1999a

Zielinska et al., 1996 U.S EPA Method TO13 ASTM D3588

heating value Ultimate Analysis (C, H, N, S,IASTM D3176

O, ash), hydrocarbon speciation

3 -2

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1 l:oo 12:oo 13:OO 14:OO 15:OO 16:OO 17:OO 18:OO 19:OO 20:oo 21:oo 9:OO 1o:oo

1 l:oo 12:oo 13:OO 14:OO 15:OO 16:OO 17:OO 18:OO 19:OO 8:OO 9:OO 1o:oo

1 l:oo 12:oo 13:OO 14:OO 15:OO 16:OO 17:OO 18:OO 19:OO 20:oo 21:oo 8:OO 9:OO 1o:oo

1 l:oo 12:oo 13:OO 14:OO 15:OO

P/10:58-11:23 R1/13:59

P/8:58 - 9:25 R2/10:41

I

16:41 P/17:14-17:45

P/8: 15-8:49

R3/11:26

I

17:26 P/18:20-19:04

1

R1/13:50

15:52 - 16:22 17:30 - 18:OO 19:50

1

Ti

13:35 - 14:05 16:40

1

Ambient Air

Figure 3-1 Chronology for Gas-Fired Process Heater Tests (Refinery Site B)

3-3

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`,,,,`,-`-`,,`,,`,`,,` -Y

P

7

12 t

1 Primary In-Stack Filter (50-80 pm 12 Sample Bypass Discharge

4 sintered stainless steel) 13 Secondarv Moisture Removal Svstem

, 1 7

3 Probe (Heated) (248*25"F) 15 Pressure Gauge To 5

4 Calibration Bias Valve 16 Unheated TFE sample line 6a Sample Line (Heated) (248*25"F)

6b Primary moisture removal system 6c Ice bath

6d Condensate removal pump 6e Thermocouple (exhaust gas <37"F) 6f Unheated Teflon line

7 Vacuum Gauge

8 Secondary Filter (Heated) (Balston,

18 Multi-Channel Stripchart Recorder

Note: The CEMS is equipped with dual

oxygen a d NO^ maipers (not shown)

for measurement of these species at a

checks)

5 pm, 25OOF)

9 TFE Diaphragm Pump 27 Check Valve second location (e.g., for stratification Oz CO2 CO NO SO2 Nz

10 Sample Bypass Regulator (Heated)

Figure 3-2 Continuous Emissions Monitoring System

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`,,,,`,-`-`,,`,,`,`,,` -Table 3-2 CEMS Instrumentation Used For Gas-Fired Process Heater Test (Refinery Site B)

Oxides of nitrogen Thermo- Electron Model 1OAR with molybdenum NOz converter Chemi- luminescence

Carbon monoxide Thermo- Electron Model 48H (CO)

Gas filter correlation infrared absorption ppmv 0.5 ppm

o- 1 O0

Model Number Model 1400

Detection principal Paramagnetism

Units measured Detection limit 0.10%

Ranges

Carbon dioxide ACS (COZ)

Model 3300

Non-dispersive infrared absorption (NDIR) 0.10%

0-20

dioxide

Ultraviolet absorption (UV)

7 o- 1 O0

minimum of contact area to avoid loss of the water soluble gas fraction The condensate was

removed with a peristaltic pump through the bottom of the heat exchanger All components in

contact with the sample were constructed of inert materials such as glass, stainless steel, and

tetrafluoroethylene (TFE) All components preceding the condenser (probe, sample line, sample

bypass regulator, and pump) were heated to 248" F to prevent condensation The sample was

conducted from the chiller outlet through the TFE line to a tertiary filter preceding the sample

manifold Samples were analyzed for O2 and CO2 using instrumental methods according to EPA

Method 3A Oxygen was measured using a paramagnetic analyzer and CO2 was measured using

a non-dispersive infrared (NDIR) analyzer Samples were analyzed for NO, using a low-

pressure chemiluminescence analyzer with a molybdenum nitrogen dioxide (NOz)-to-nitric oxide

(NO) converter according to EPA Method 7E Sulphur dioxide was determined in the sample

using a non-dispersive ultraviolet analyzer according to EPA Method 6C Carbon monoxide was

determined using a NDIR analyzer following EPA Method 1 O

IN-STACK METHOD TESTS

Total particulate, PM10 and PM2.5 filterable at stack temperature were determined using in-

stack methods CPM, defined as the material collected in chilled impingers, also was measured

for the in-stack samples

3-5

Not for Resale

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`,,,,`,-`-`,,`,,`,`,,` -In-Stack Total Filterable PM PM10 and PM2.5

Two in-stack cyclones followed by an in-stack filter (Figure 3-3) were used to measure total

particulate and particulate matter with nominal aerodynamic diameters less than or equal to 10

pm (PM10) and 2.5 pm (PM2.5) EPA Method 201A, modified to accommodate the second cyclone, was used following the constant-rate sampling procedure Sampling time was six hours for each of the three runs The sample recovery field procedure is summarized in Figure 3-4 Sampling was performed as published except for the following modifications and clarifications:

A PM 1 O cyclone and a PM2.5 cyclone (Andersen Model Case-PM 1 O and

Case-PM2.5) were attached in series to the filter inlet Sample recovery procedures were modified accordingly;

The sample was collected £rom a single traverse point near the center of the stack to preserve the integrity of the dilution tunnel method comparison It was assumed that any particulate present was small enough to mix

aerodynamically in the same manner as a gas; therefore, the magnitude of the particle concentration profile was assumed to be no greater than the gas concentration profile Quartz filters were used The filters were

preconditioned in the same manner as those used in the dilution tunnel, as described below; and

A modified filter assembly was employed in an effort to improve the precision

of the gravimetric analysis for low particulate concentration

The particulate mass collected in the two cyclones and on the filter was determined

gravimetrically (Figure 3-5) The filters (Pallflex No 5 1575) were weighed before and after testing on an analytical balance with a sensitivity of 10 micrograms In an effort to improve the accuracy and precision of the gravimetric results, the filters, filter support and metal O-ring seals were weighed together to minimize post-test loss of filter matter during sample recovery Pre- and post-test weighing was performed after drying the filters in a dessicator for a minimum

of 72 hours; repeat weighings were then performed at a minimum of 6-hour intervals until constant weight was achieved Probe and cyclone acetone rinses were recovered in glass

sample jars for storage and shipment, then transferred to tared Teflon@ beaker liners for

evaporation and weighing Acetone and filter blanks also were collected and analyzed See

Section 4 for discussion of data treatment

3-6

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`,,,,`,-`-`,,`,,`,`,,` -Series cyclones and filter (in- stack) Thermocouple

Filter

/

S-Type Pitot Tube

Sampling train

Impinger Configuration

1 Greenburg-Smith, 100 ml DI water

2 Greenburg-Smith, 100 ml DI water

3 Modified Greenburg-Smith, empty

4 Modified Greenburg-Smith, silica gel

Not for Resale

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`,,,,`,-`-`,,`,,`,`,,` -Disassemble PM10 cyclone

Remove nozzle

acetone

Final rinse of brush and interior surfaces

acetone

acetone 3 times

particulate removed; if not,

A

Disassemble 47mm Gelman filter housing

Recover all internal surfaces from PM2.5 :yclone exit through filtei support

acetone 3 times

Inspect to see if all particulate removed; if not,

and interior surfaces

Particles <2.5 pm caught in-stack filter”

Tiêu đề	Gas Fired Heater-Test Report Site B Characterization of Fine Particulate Emission Factors and Speciation Profiles from Stationary Petroleum Industry Combustion Sources Regulatory and Scientific Affairs
Tác giả	Karin Ritter, Lee Gilmer, Karl Loos, Jeff Siegell, Glenn England, Stephanie Wien, Bob Zimperman, Barbara Zielinska, Jake McDonald
Thể loại	report
Năm xuất bản	2001
Thành phố	Washington, D.C.

Định dạng
Số trang	118
Dung lượng	4,62 MB